Process for the removing poly(propylene oxide) from propylene oxide by membrane separation

ABSTRACT

The invention relates to a process for removing poly(propylene oxide) from propylene oxide by membrane separation, wherein a membrane having an average pore size of from 0 to 5 nm is used. In said process, a liquid feed comprising propylene oxide and poly(propylene oxide) may be separated by the membrane into a permeate comprising propylene oxide and either no poly(propylene oxide) or poly(propylene oxide) at a concentration which is lower than the poly(propylene oxide) concentration in the feed, and a retentate comprising propylene oxide and poly(propylene oxide) at a concentration which is higher than the poly(propylene oxide) concentration in the feed.

The present application claims priority from European Patent Application06126675.5 filed 20 Dec. 2006.

FIELD OF THE INVENTION

The present invention relates to a process for removing poly(propyleneoxide) from propylene oxide by membrane separation.

BACKGROUND OF THE INVENTION

Propylene oxide is widely used as precursor for preparing polyetherpolyols, which upon reaction with polyisocyanate compounds yieldpolyurethanes. Typically, methods for preparing polyether polyolsinvolve reacting a starting compound having a plurality of activehydrogen atoms with propylene oxide, optionally together with one ormore other alkylene oxides like ethylene oxide or butylene oxide.Suitable starting compounds include polyfunctional alcohols, generallycontaining 2 to 6 hydroxyl groups. Examples of such alcohols areglycols, glycerol, pentaerythritol, trimethylolpropane, triethanolamine,sorbitol, mannitol, etc. Usually a strong base like potassium hydroxideis used as a catalyst in this type of reaction.

The quality of the propylene oxide used to prepare the polyether polyolhas significant impact on the quality of the polyurethane foamseventually obtained, especially when these foams are high resilienceflexible polyurethane foams. Particularly the presence of poly(propyleneoxide) is known to cause undesired effects in the polyurethane foamformation. Examples of such undesired effects are the occurrence of blowholes, low foam rise and even collapse of the foam formed. Particularly,in moulding applications, the presence of poly(propylene oxide) in thepropylene oxide used for preparing the starting polyether polyol maycause problems in terms of quality of the polyurethane foam. Thepresence of poly(propylene oxide) in propylene oxide used for preparinga polyether polyol for making slabstock polyurethane foams, may be lessproblematic.

In producing slabstock polyurethane foams, slabs of polyurethane foamare produced continuously or discontinuously as semi-finished productsand are finally cut to the required size and shape. The characteristicfeature of moulded polyurethane foams in which they fundamentally differfrom slabstock polyurethane foams, is the manner of their production.This proceeds by reaction of the polyurethane raw materials in moulds.The finished moulded product no longer has to be cut to the requiredsize and shape. For a further description of the differences betweenslabstock and moulded polyurethane foams, reference is made to handbookson polyurethane foams, such as “Polyurethane Handbook/Chemistry—RawMaterials—Processing—Application—Properties” by Günter Oertel (CarlHanser Verlag, Munich 1985).

It has appeared in practice that, in general, where propylene oxide isto be used to prepare a polyether polyol for making moulded polyurethanefoams, no more than 1 ppm of poly(propylene oxide) should be present insaid propylene oxide. If more propylene oxide is present, one or more ofthe above-mentioned undesired effects may occur when making the foam. Onthe other hand, where propylene oxide is to be used to prepare apolyether polyol for making slabstock polyurethane foams, in general, upto 3 ppm of poly(propylene oxide) may be present in the propylene oxide.

Methods for manufacturing propylene oxide are well known in the art.Commercial production normally takes place via the chlorohydrin processor via the hydroperoxide process. In the latter process propene isreacted with an organic hydroperoxide. This hydroperoxide is eithertert-butyl hydroperoxide or ethylbenzene hydroperoxide. In the firstcase tert-butyl alcohol is formed as a co-product (to be furtherconverted into methyl tert-butyl ether), in the second case styrene isformed as the co-product. In the chlorohydrin process chlorine, propeneand water are reacted to form propylene chlorohydrin, which issubsequently dehydrochlorinated with calcium hydroxide to form propyleneoxide. For the purpose of the purification of propylene oxide it isimmaterial which preparation route is used. Namely, in all processespoly(propylene oxide) is formed in undesirably high quantities.Moreover, it is known (e.g. from U.S. Pat. No. 4,692,535) that highmolecular weight poly(propylene oxide) may be formed during storage ortransport, for example upon contact with a metal and/or metal oxide,such as metal oxide of carbon steel.

One method for purification of propylene oxide by membrane separation isknown from U.S. Pat. No. 5,248,794. According to this method, suitablemembranes are poly(vinylidene fluoride) and poly(acrylonitrile)polymeric membranes. Such polymers are commonly used in the art asmaterials for ultrafiltration membranes. See for example Table II.12 atpage 56 of “Basic Principles of Membrane Technology”, Marcel Mulder,second edition, Kluwer Academic Publishers, 1996. In said Table II.12,poly(vinylidene fluoride) and poly(acrylonitrile), but also polysulfoneand cellulose esters, are mentioned as examples of polymers forultrafiltration membranes. Therefore, the membranes disclosed in U.S.Pat. No. 5,248,794 are ultrafiltration membranes. Ultrafiltrationmembranes are porous membranes which have an average pore size greaterthan 5 nm.

In Table 2 of Example 1 of U.S. Pat. No. 5,248,794, poly(propyleneoxide) separation results are mentioned for some different types ofmembranes. The poly(propylene) membranes were not considered suitable.Only the poly(vinylidene fluoride) and poly(acrylonitrile)ultrafiltration membranes were considered suitable for the purpose ofU.S. Pat. No. 5,248,794. One way of determining the suitability of amembrane for separating poly(propylene oxide) (PPO) from propyleneoxide, is by calculating the PPO rejection, as follows:PPO rejection (%)=(1−([PPO]_(p)/[PPO]_(f)))*100wherein [PPO]_(p) is the poly(propylene oxide) concentration in thepermeate and [PPO]_(f) is the poly(propylene oxide) concentration in thefeed. Where in the present specification reference is made to PPOrejection, the PPO rejection defined in the above way is meant.

In Example 1 of U.S. Pat. No. 5,248,794, using poly(propylene) membranesresulted in a negative PPO rejection. Further, using poly(vinylidenefluoride) and poly(acrylonitrile) ultrafiltration membranes resulted inrelatively low PPO rejections (<30%). The poly(propylene oxide)concentrations in the permeates as mentioned in Table 2 of U.S. Pat. No.5,248,794, are so high that these permeates cannot be used in theproduction of moulded polyurethane foams and neither in the productionof slabstock polyurethane foams.

Further, in Example 2 of U.S. Pat. No. 5,248,794, the samepoly(acrylonitrile) membrane as used in Example 1, was tested with acontinuous flow of unfiltered propylene oxide over a period of 86 days.The results are listed in Table 3 of U.S. Pat. No. 5,248,794. From thisit appears that in the course of time, the PPO rejection increases froma value of only 31% (on day 1) to a maximum of 100% (on days 52 and 55)and then decreases again to a value of only 67% (on day 86). Therefore,the membrane used is disadvantageous in that there is a relatively longwaiting period (of about 52 days) before permeate is produced of whichthe quality is such that it can be used in the production of mouldedpolyurethane foams and slabstock polyurethane foams. Further, after day55, permeate of inferior quality is produced again. Besides a low andunstable PPO rejection in time, another disadvantage is that thepermeate flow is also unstable. In said Example 2, the permeate flowgoes from a maximum value of 90 ml/min. at the beginning of theexperiment, to a value of only 37 ml/min. at the end. This indicatesthat the membrane, being a porous poly(acrylonitrile) ultrafiltrationmembrane, gets clogged or plugged in the course of time.

In summary, both the selectivity of and the flow (flux) through themembrane used in Example 2 of U.S. Pat. No. 5,248,794 are relatively lowand unstable in time. The volume or mass “flux” (volume or mass“permeation rate”) is defined as the volume or mass flowing through themembrane per unit area and time (expressed in l/h/m² and kg/h/m²,respectively). The permeability of a membrane is defined as the fluxthrough the membrane per unit pressure, and is expressed in l/h/m²/baror kg/h/m²/bar. When performing the process of U.S. Pat. No. 5,248,794,a strong fluctuation of separation results in time is obtained. This isdisadvantageous in that it is difficult to predict whether or not acertain specification, for example a maximum poly(propylene oxide)concentration in PO permeate, can be met on a certain day.

A further method for improving the quality of propylene oxide bymembrane separation is known from GB-A-2348200. In this method, liquidpropylene oxide is subjected to a treatment using a ceramicultrafiltration (porous) membrane under such conditions that the amountof poly(propylene oxide) is reduced. In the Example of GB-A-2348200, aceramic ultrafiltration membrane having a pore size of 6 nm was used inseparating poly(propylene oxide) from propylene oxide. In said Example,it is stated that it was found that said membrane removed about 50%poly(propylene oxide). More in particular, it appears that in saidExample, the poly(propylene oxide) concentration in the propylene oxidefeed was 1.03 mg/l and that the poly(propylene oxide) concentration inthe permeate was still 0.54 mg/l. This corresponds with a PPO rejectionof only 48%.

In the above-discussed prior art methods for removing poly(propyleneoxide) from propylene oxide by membrane separation, ultrafiltrationmembranes are used. Ultrafiltration is a pressure difference drivenmembrane filtration technique, wherein porous membranes are used whichhave an average pore size greater than 5 nm. One of the disadvantages ofusing ultrafiltration membranes as discussed above, is that themembranes foul during operation (membrane pores getting clogged orplugged) and have eventually to be taken out of operation for cleaningpurposes. This will severely decrease the separation efficiency in time.A further disadvantage of using polymeric ultrafiltration membranes, isthat they swell. Swelling has an effect on the pore size and results inpermeability and selectivity instability.

In summary, from the above discussion of prior art methods for removingpoly(propylene oxide) from propylene oxide by membrane separation, itappears that there is still a need in the art for a process using amembrane which, during a relatively long period of time, can separatepoly(propylene oxide) from propylene oxide, in a stable way, both interms of a stable PPO rejection and in terms of a stable permeate flow.In addition, this constant, stable PPO rejection should be sufficientlyhigh such that the permeate produced at any time, can be used forexample in the production of moulded polyurethane foams and/or slabstockpolyurethane foams.

SUMMARY OF THE INVENTION

It is the object of the present invention to fulfil said need and toprovide a process for removing poly(propylene oxide) from propyleneoxide by membrane separation, which does not have the disadvantages ofthe prior art processes as discussed above. This object is achieved byusing a membrane which is a non-porous (no pores) or nanofiltration(pores having an average size of at most 5 nm) membrane. As furtherdiscussed below, such non-porous and nanofiltration membranes arecommonly referred to in the art as dense membranes and work in a similarway. Accordingly, the process according to the present invention is aprocess for removing poly(propylene oxide) from propylene oxide bymembrane separation, wherein a membrane having an average pore size offrom 0 to 5 nm is used.

DETAILED DESCRIPTION OF THE INVENTION

Preferably, the membrane to be used in the present invention isresistant to hydrocarbons, such as propylene oxide. This implies thatthe membrane does not dissolve in the propylene oxide which it has topurify.

In general, in a process for removing poly(propylene oxide) frompropylene oxide by membrane separation, a liquid feed comprisingpropylene oxide and poly(propylene oxide) is separated by the membraneinto a permeate comprising propylene oxide and either no poly(propyleneoxide) or poly(propylene oxide) at a concentration which is lower thanthe poly(propylene oxide) concentration in the feed, and a retentatecomprising propylene oxide and poly(propylene oxide) at a concentrationwhich is higher than the poly(propylene oxide) concentration in thefeed.

Applicants have found that when using a non-porous or nanofiltrationmembrane, very good and stable separation results are obtained in suchprocess for removing poly(propylene oxide) from propylene oxide. Forexample, less fouling of the membrane occurs and therefore the membranehas to be taken out of operation less frequently than when using anultrafiltration membrane as in the above-discussed prior art processes.Therefore, the present process can be performed efficiently on acontinuous basis.

The use of a non-porous or nanofiltration membrane in purifyinghydrocarbons in general, is described in WO-A-01060771 (which is in thename of Shell). This document discloses a process for purifying a liquidhydrocarbon product comprising 5% by weight or less of high molecularweight contaminants having a molecular weight of at least 1000, whereinthe product stream is contacted with a non-porous or nanofiltrationmembrane and the purified product stream is recovered as the permeate.Although there is no specific limitation as to the nature of the liquidhydrocarbon product in WO-A-01060771, the products specificallymentioned are typically industrially produced chemical product streamscontaining a polymerisable olefinic bond. The products may include oneor more heteroatoms, and named examples of liquid hydrocarbon productsinclude hydrocarbon per se, such as cyclopentadiene, dicyclopentadiene,1,3-cyclohexadiene, cyclohexene, styrene, isoprene, butadiene,cis-1,3-pentadiene, trans-1,3-pentadiene, benzene, toluene, xylenes,ethene and propene. Named liquid hydrocarbon products containingheteroatoms are methyl acrylate, ethyl acrylate and methylmethacrylate.However, there is no mention in WO-A-01060771 of purification of apropylene oxide stream comprising poly(propylene oxide) by means of anon-porous or nanofiltration membrane.

The non-porous or nanofiltration membrane to be used in the presentinvention may be of the ceramic or polymeric type. Preferably, themembrane used is hydrophobic because the stream to be treated is ahydrocarbon stream which should be capable of passing through themembrane. An additional advantage of using a hydrophobic membrane ratherthan a hydrophilic one, is that using a hydrophobic membrane willprevent water from passing the membrane and entering the permeate. It iswell known that water may initiate polymerisation of propylene oxide,resulting in a polyol, which is undesired.

Non-porous and nanofiltration membranes are commonly referred to in theart as dense membranes. Examples of non-porous and nanofiltrationmembranes are reverse osmosis type membranes. Non-porous andnanofiltration membranes should be distinguished from ultrafiltrationmembranes which are always porous. Ultrafiltration membranes have anaverage pore size of greater than 5 nm up to about 800 nm. Wherenanofiltration membranes are used which are porous, they have an averagemembrane pore size which is at most 5 nm (nanoporous membranes). Wheresuch nanofiltration or nanoporous membrane is used in accordance withthe present invention, the average membrane pore size is suitably lessthan 5 nm, preferably at most 3 nm, more preferably at most 2 nm, morepreferably at most 1 nm, more preferably at most 0.7 nm, more preferablyat most 0.5 nm, more preferably at most 0.3 nm, more preferably at most0.1 nm, more preferably at most 0.05 nm, and most preferably at most0.01 nm.

The term “poly(propylene oxide)” as used throughout the presentspecification in relation to the present invention, refers topoly(propylene oxide) having a molecular weight of 1500 Dalton orhigher, or having a molecular weight of 1000 Dalton or higher, or havinga molecular weight of 900 Dalton or higher, or having a molecular weightof 750 Dalton or higher, or having a molecular weight of 500 Dalton orhigher, unless stated otherwise. The molecular weights as usedthroughout this specification are expressed in Dalton (1 Da=1 g/mole)and are based on a determination by size-exclusion chromatography (SEC)as is further explained in the present Examples.

Non-porous and nanofiltration membranes as such are known in the art andin principle any non-porous or nanoporous membrane capable of retaining80% by weight or more, preferably 90% by weight or more, most preferably95% by weight or more, and very highly preferably 99% by weight or moreof the poly(propylene oxide), can be used in the present invention. Theupper limit for the molecular weight of the poly(propylene oxide) to beremoved, is not critical and may be as high as 500,000.

In a preferred embodiment of the present invention, the non-porous ornanofiltration membrane is a polymeric membrane. Such polymeric membraneis preferably cross-linked to provide the necessary network for avoidingdissolution of the membrane once being in contact with propylene oxide.In general, cross-linking can be effected in several ways, for instanceby reaction with cross-linking agents (chemical cross-linking) and/or byirradiation. Preferably, the membrane layer has a siloxane structurewhich has been cross-linked by means of irradiation, as is for exampledescribed in WO-A-9627430.

Examples of suitable, presently available cross-linked non-porous ornanofiltration membranes are cross-linked silicone rubber-basedmembranes, of which the cross-linked polysiloxane membranes are aparticularly useful group of membranes. Such cross-linked polysiloxanemembranes are known in the art, for example from U.S. Pat. No.5,102,551.

Typically, the polysiloxanes used contain the repeating unit —Si—O—,wherein the silicon atoms bear hydrogen or a hydrocarbon group.Preferably the repeating units are of the formula (I)—Si(R)(R′)—O—  (I)wherein R and R′ may be the same or different and represent hydrogen ora hydrocarbon group selected from the group consisting of alkyl,aralkyl, cycloalkyl, aryl, and alkaryl. Preferably, at least one of thegroups R and R′ is an alkyl group, and most preferably both groups arealkyl groups, more especially methyl groups. The alkyl group may also bea 3,3,3-trifluoropropyl group. Very suitable polysiloxanes for thepurpose of the present invention are (—OH or —NH₂ terminated)polydimethylsiloxanes and polyoctylmethylsiloxanes. Thus, preferably,the polysiloxane is cross-linked. The cross-linking may be effectedthrough a reactive terminal —OH or —NH₂ group of the polysiloxane.Preferred polysiloxane membranes are cross-linked elastomericpolysiloxane membranes.

Examples of suitable cross-linked elastomeric polysiloxane membranes areextensively described in above-mentioned U.S. Pat. No. 5,102,551. Thus,suitable membranes are composed of a polysiloxane polymer such asdescribed supra having a molecular weight of 550 to 150,000, preferably550 to 4200 (prior to cross-linking), which is cross-linked with, ascross-linking agent, (i) a polyisocyanate, or (ii) a poly(carbonylchloride) or (iii) R_(4-a)Si(A)_(a) wherein A is —OH, —NH₂, —OR, or—OOCCR, a is 2, 3, or 4, and R is hydrogen, alkyl, aryl, cycloalkyl,alkaryl, or aralkyl. Further details regarding suitable polysiloxanemembranes can be found in U.S. Pat. No. 5,102,551.

For the purpose of the present invention the preferred non-porousmembrane is a polydimethylsiloxane membrane, which is preferablycross-linked. Also other rubbery non-porous membranes could be used. Ingeneral, rubbery membranes can be defined as membranes having anon-porous top layer of one polymer or a combination of polymers, ofwhich at least one polymer has a glass transition temperature well belowthe operating temperature, i.e. the temperature at which the actualseparation takes place. Yet another group of potentially suitablenon-porous membranes are the so called superglassy polymers. An exampleof such a material is poly(trimethylsilylpropyne).

The non-porous or nanofiltration membrane is typically supported on atleast one porous substrate layer to provide the necessary mechanicalstrength. Suitably, this other porous substrate layer is made of aporous material of which the pores have an average size greater than 5nm. Such other porous material may be a microporous, mesoporous ormacroporous material which is normally used for microfiltration orultrafiltration, such as poly(acrylonitrile). The thickness of the baselayer should be sufficiently to provide the necessary mechanicalstrength. In addition, this substrate may in return be supported on afurther porous support to provide the required mechanical strength.Typically, the thickness of the base layer is of from 100 to 250 μm,more suitably of from 20 to 150 μm. Where the non-porous ornanofiltration membrane is combined with such base layer, the membranesuitably has a thickness of from 0.5 to 10 μm, preferably of from 1 to 5μm.

The combination of a thin top membrane layer and a thick porous supportlayer is often referred to as composite membranes or thin filmcomposites. The membrane is suitably so arranged that the permeate flowsfirst through the membrane top layer and then through the base layer, sothat the pressure difference over the membrane pushes the top layer ontothe base layer. Suitable porous materials for the base layer having anaverage pore size greater than 5 nm, are poly(acrylonitrile),poly(amideimide)+TiO₂, poly(etherimide), polyvinylidenedifluoride andpoly(tetrafluoroethylene). Poly(acrylonitrile) is especially preferred.The preferred combination according to the present invention is apoly(dimethylsiloxane)-poly(acrylonitrile) combination.

The non-porous or nanofiltration membrane may also be used without asubstrate layer, but it will be understood that in such a case thethickness of the membrane should be sufficient to withstand thepressures applied. A thickness greater than 10 μm may then be required.This is not preferred from a process economics viewpoint, as such thickmembrane will significantly limit the throughput of the membrane,thereby decreasing the amount of purified product which can be recoveredper unit of time and membrane area.

When using a non-porous or dense membrane, transmission of the permeatetakes place via the solution-diffusion mechanism. The propylene oxide tobe permeated dissolves in the membrane matrix and diffuses through thethin selective membrane layer, after which it desorbs at the permeateside. The main driving force for permeation is hydrostatic pressure.Examples of such membranes are reverse osmosis type membranes. In case ananoporous membrane is used in the present invention, it is believedthat separation takes place both on the basis of the above-mentionedsolution-diffusion mechanism and on the basis of molecular sizedifferences. In the latter case, there is no question of dissolution ofthe permeate in the membrane matrix but only of transport through themembrane via its nanopores. Where such solution-diffusion mechanism isfunctioning, it is believed to be important that the membrane materialdoes not dissolve the contaminant to be removed from the membrane feedbut, preferentially, only the component that has to be freed from thecontaminant. The present inventors have found that especiallypolysiloxane membranes, for example poly(dimethylsiloxane) membranes,are capable of such preferential dissolution of propylene oxide, ratherthan poly(propylene oxide) which they do not dissolve.

An advantage of using non-porous membranes as compared to the use ofnanoporous membranes is that there is no plugging effect. This meansthat there is no possibility of the membrane becoming blocked by largermolecules plugged in the pores. This could happen in porous membranes,as a result of which it is more difficult to regenerate a stable flux.Therefore, it is preferred for the purpose of the present invention touse a non-porous or dense membrane. However, it is emphasised thatnanoporous membranes could also be used in the process of the presentinvention as a nanofiltration membrane.

The retentate will still comprise valuable propylene oxide and for thatreason the retentate may suitably be recycled to the membrane separationstep and mixed with fresh feedstock. However, when recycling retentate,part of the retentate will have to be discharged such as to avoid buildup of the poly(propylene oxide) which is to separated from the propyleneoxide by means of said membrane process. Instead of recycling theretentate within the same process, it may also be subjected to a secondand optionally further separation step, in which case the retentate of afirst separation step is used as the feed for a second separation step.

Further, instead of recycling (part of) the retentate or furtherpurifying it in a second and optionally further step, the retentate mayalso be discharged in its entirety. This is most likely advantageouswhere the composition of the retentate is such that it has some value asa starting material in another process, without having to further treatthe retentate before such use (no further processing). The permeate hasbeen upgraded in the sense that its contamination level has beenlowered. Consequently the permeate has obtained a higher value comparedto the original product. The retentate, which contains an increasedproportion of poly(propylene oxide) as compared to the original product,has a value depending on the poly(propylene oxide) concentration and theperceived end use. The retentate value may be lower than or similar tothe value of the original feed.

Stage cut is defined as the weight percentage of the original feed thatpasses through the membrane and is recovered as permeate. By adjustingthe stage cut, it is possible to vary the concentration of a contaminantin the permeate, as well as the concentration of said same contaminantin the retentate. The higher the stage cut, the higher the contaminantconcentration in the retentate.

In the present invention, the stage cut can vary within broad limits: 10to 99% by weight, suitably 30 to 95% by weight or 50 to 90% by weight.All that matters is that a poly(propylene oxide) concentration inpermeate and/or retentate is achieved which is below a certain maximum.For example, where it is intended to use the permeate in the productionof moulded polyurethane foam, a relatively high stage cut might have tobe achieved. Another relevant factor to consider is the poly(propyleneoxide) concentration in the feed.

The desired stage cut can be set by varying, for a given permeability ofthe membrane, the trans-membrane pressure and/or the feed flow. Thefirst option implies that, for a given feed flow, increasing thetrans-membrane pressure results in a greater flux or flow of thepermeate through the membrane, and therefore in a higher stage cut.According to the second option, such higher stage cut may also beachieved by decreasing the feed flow whilst maintaining a certainpermeate flow through the membrane.

In the present invention, the volume flux through the membrane istypically in the range of from 5 to 1000, suitably 10 to 500, and moresuitably 15 to 200 l/h/m². The flux through the membrane may also beexpressed as mass flux. Preferably, the flux through the membrane isconstant in time. Further, the inlet stream is contacted with themembrane at a trans-membrane pressure (pressure difference) which istypically in the range of from 1 to 60 bar, suitably 3 to 35 bar, andmore suitably 3 to 25 bar. The permeability of the membrane is typicallyin the range of from 1 to 100, suitably 2 to 50, and more suitably 3 to10 l/h/m²/bar.

In accordance with the present invention, a liquid feed comprisingpropylene oxide and poly(propylene oxide) may be separated by anon-porous or nanofiltration membrane into a permeate comprisingpropylene oxide and either no poly(propylene oxide) or poly(propyleneoxide) at a concentration which is lower than the poly(propylene oxide)concentration in the feed, and a retentate comprising propylene oxideand poly(propylene oxide) at a concentration which is higher than thepoly(propylene oxide) concentration in the feed.

Preferably, the poly(propylene oxide) concentration in said permeate isfrom essentially zero to at most 10 ppmw (parts per million by weight),more preferably at most 5 ppmw, more preferably at most 3 ppmw, morepreferably at most 1 ppmw, more preferably at most 0.5 ppmw, morepreferably at most 0.3 ppmw, and most preferably at most 0.1 ppmw, onthe basis of total weight of the permeate. Such permeate may suitably beused as raw material in making a polyether polyol to be used in makingslabstock polyurethane foam.

Further, preferably, the poly(propylene oxide) concentration in saidpermeate is from essentially zero to less than 1 ppmw, more preferablyfrom essentially zero to 0.5 ppmw, more preferably from essentially zeroto 0.3 ppmw, and most preferably from essentially zero to 0.1 ppmw, onthe basis of total weight of the permeate. Such permeate may suitably beused as raw material in making a polyether polyol to be used in makingeither slabstock polyurethane foam or moulded polyurethane foam.

In particular, where propylene oxide is to be used in making mouldedpolyurethane foam, the concentration of poly(propylene oxide) having amolecular weight of 20,000 and higher, in such propylene oxide, shouldpreferably not exceed 0.5 ppmw. More preferably, the concentration ofsaid higher molecular weight poly(propylene oxide) is at most 0.4 ppmw.

Preferably, the poly(propylene oxide) concentration in said retentate isfrom essentially zero to at most 20 ppmw, more preferably at most 10ppmw, more preferably at most 5 ppmw, more preferably at most 3 ppmw,and most preferably at most 2 ppmw, on the basis of total weight of theretentate. Such retentate may suitably be used as raw material in makinga polyether polyol to be used in making slabstock polyurethane foam.

Thus, a further advantage is that in addition to the permeate, theretentate can also have some end use value as long as the stage cut isproperly controlled.

The membrane separation will be performed in a membrane unit, whichcomprises one or more membrane modules. Examples of suitable modules aretypically expressed in how the membrane is positioned in such a module.Examples of these modules are the spirally wound, plate and frame (flatsheet), hollow fibres and tubular modules. Preferred moduleconfigurations are spirally wound and plate and frame. Most preferably,the non-porous or nanofiltration membrane is applied in a membrane unit,which comprises spirally wound membrane modules. These membrane modulesare well known to the skilled person as for example described inEncyclopedia of Chemical Engineering, 4^(th) Ed., 1995, John Wiley &Sons Inc., Vol 16, pages 158-164. Examples of spirally wound modules aredescribed in for example, U.S. Pat. No. 5,102,551, U.S. Pat. No.5,093,002, U.S. Pat. No. 5,275,726, U.S. Pat. No. 5,458,774, U.S. Pat.No. 5,150,118, and WO-A-2006040307.

It will be appreciated that preferably the operating temperature shouldbe kept below the boiling point of the propylene oxide feed in order tohave a liquid inlet stream. The boiling point of propylene oxide isabout 34° C. Thus, at atmospheric pressure temperatures from 0° C. up to34° C. may be applied. Suitably, the separation is carried out at atemperature in the range of from 5 to 30° C., more suitably at ambienttemperature.

The way in which the propylene oxide to be purified in accordance withthe present invention is prepared, is immaterial to the presentinvention. Any known preparation process may have been applied. Thepropylene oxide to be treated in the process according to the presentinvention may be the product directly obtained from the knownpreparation processes. Alternatively, said directly obtained propyleneoxide also may have been subjected to conventional purification andrecovery techniques before it is treated in accordance with the presentinvention. Assuming that the propylene oxide is produced in ahydroperoxide process, such purification and recovery techniquestypically involve the removal of unreacted propene and organichydroperoxide, by-products (like propane, aldehydes and alcohol) andother treating agents. Typically, the propylene oxide feed to bepurified in the present process, has been obtained by the epoxidation ofpropene using ethylbenzene hydroperoxide as the oxidant, then separatingpropene from the product mixture comprising propylene oxide and methylphenyl carbinol, and finally separating propylene oxide from the methylphenyl carbinol.

In general, the propylene oxide stream to be treated in the process ofthe present invention comprises at least 95 wt % of propylene oxide.

If the propylene oxide product to be treated is a relatively crudepropylene oxide stream, such product may contain 5% by weight or less ofpoly(propylene oxide) based on total weight of the product. However, thepresent method is particularly suitable when the propylene oxide productto be treated contains 3% by weight or less, suitably 1% by weight orless, and more suitably 0.1% by weight or less of the poly(propyleneoxide). Even at such relatively high poly(propylene oxide) levels, theprocess of the present invention is highly effective.

If the propylene oxide product to be treated is a relatively purepropylene oxide stream, such product preferably contains less than 500ppmw, suitably less than 300 ppmw, more suitably less than 200 ppmw,more suitably less than 100 ppmw, more suitably less than 50 ppmw, andmost suitably less than 20 ppmw of poly(propylene oxide). Typically,such relatively pure propylene oxide inlet stream comprises 1 to 15 ppmwof poly(propylene oxide).

The invention is further illustrated by the following Examples.

EXAMPLE 1 AND COMPARATIVE EXAMPLES 1 AND 2

Poly(propylene oxide) (PPO) was removed from a propylene oxide (PO) feedby using a dead-end membrane unit. In a dead-end membrane unit, the feedflows perpendicular to the membrane surface. The experimental set-upused in these examples is schematically shown in FIG. 1, wherein thereference numerals have the following meanings:

1: stirrer 2: nitrogen inlet 3: PO/PPO feed mixture 4: membrane 5:permeate outlet 6: collection vessel

In these examples, the pressure difference over membrane 4 of thedead-end membrane unit of FIG. 1, necessary for effecting the flow ofpermeate through the membrane, was applied by means of pressurisation byfeeding nitrogen gas via nitrogen inlet 2. In addition, the nitrogen wasused as a blanket covering PO/PPO feed mixture 3. The trans-membranepressure applied was 5 bar during the entire experimental period.

After having applied said trans-membrane pressure, the vessel shown inFIG. 1 was filled with 140 grams of the PO/PPO feed. Subsequently,stirring of this feed under a blanket of nitrogen gas was started byusing stirrer 1. Said stirring was carried out during a time period of75 minutes at which time about 70 grams of the original feed hadpermeated through the membrane. The stage cut was therefore about 50 wt.%. The temperature during the entire experimental period was roomtemperature.

In Example 1, a supported membrane was used wherein the top layer havinga thickness of approximately 3 μm was made of hydrophobic non-porous(dense) cross-linked poly(dimethylsiloxane) (PDMS). The total membranesurface was 5 cm².

In Comparative Examples 1 and 2, different types of membranes were used,namely ultrafiltration porous membranes having a pore size greater than5 nm and being made of either poly(acrylonitrile) (PAN) orpoly(vinylidene fluoride) (PVDF), as disclosed in U.S. Pat. No.5,248,794 which is discussed in the introduction of this specification.

In Comparative Example 1, a supported membrane was used wherein the toplayer having a thickness of approximately 3 μm was made of hydrophobicporous poly(acrylonitrile) (PAN) having an average pore size of 25 nm.The total membrane surface was 5 cm².

In Comparative Example 2, a supported membrane was used wherein the toplayer having a thickness of approximately 3 μm was made of hydrophobicporous poly(vinylidene fluoride) (PVDF) having an average pore size of20 nm. The total membrane surface was 5 cm².

At the end of the above-mentioned time period, the part of the PO/PPOfeed mixture which remained inside the vessel and which did not passthrough the membrane as the permeate, was decanted and recovered as theretentate. The PPO concentrations in the retentate and the permeate weredetermined. These PPO concentrations are shown in Table 1, as well asthe PPO concentration of the feed at the beginning of the experiment.

The PPO concentrations were determined by means of combinedsize-exclusion chromatography (SEC) and refractive index detection. Atest sample of propylene oxide is evaporated and the residue thusobtained is dissolved in tetrahydrofuran (THF). An aliquot of thesolution thus obtained is injected onto a SEC column. The molecules areseparated according to their hydrodynamic volume (so-called size) insolution. The separated molecules are detected by a high sensitivitydifferential refractive index (dRI) detector and recorded as they elutefrom the column according to concentration. From the molecular weightdistribution of the residue thus obtained, the fraction of highmolecular weight PPO is identified using a polystyrene standard (PS)having an average molecular weight of 20,000 Da. For the quantificationof this fraction, a poly(propylene glycol) (PPG) standard having anaverage molecular weight of 5,000 Da is applied, using a multi-pointexternal standard calibration technique. The concentration (in mg/l) ofthe high molecular weight PPO (PS 20,000 Da and higher) in the samplewas calculated by means of the following equation:C_(cal)*V_(THF)/V_(PO)where:

C_(cal)=concentration of the high molecular weight PPO in test solutionas obtained from the calibration graph (in mg/l);

V_(THF)=total volume of THF added for dilution of residue; and

V_(PO)=total volume of PO evaporated from test sample.

TABLE 1 Comp. Comp. Ex. 1 Ex. 1 Ex. 2 PPO concentration in feed 273 273273 (ppmw) PPO concentration in <1 22 61 permeate (ppmw) PPO rejection(%) >99 92 78 PPO concentration in 746 493 409 retentate (ppmw)

From Table 1 it can be seen that the PPO rejection in Example 1 ishigher than in Comparative Examples 1 and 2. The permeate obtained inExample 1, having a concentration of PPO having a molecular weight of20,000 and higher, of less than 1 ppmw, may suitably be used as rawmaterial in making a polyether polyol to be used in making moulded orslabstock polyurethane foam.

Still further, it was found that after having decanted the retentate,the membrane used in Example 1 could be used again to treat anotherPO/PPO batch at a similar flux resulting in a similar PPO rejection asin said Example 1. This implies that after use, the separation qualityof the membrane used in Example 1 remains the same.

EXAMPLES 2 AND 3

A spiral wound membrane module similar to the one as shown in FIG. 1 ofWO-A-2006040307 and as further described therein, was used, with theproviso that the module was made PO resistant, inter alia by using POresistant spacers and seals, and that the membrane used was the same asthe membrane used in Example 1 of the present specification. For a moredetailed description of said module and the operation of it, referenceis made to WO-A-2006040307.

In using a spiral wound membrane module, the feed flows parallel to themembrane surface with the inlet feed stream entering the membrane moduleat a certain composition (cross-flow operation). The feed compositioninside the module changes as a function of distance in the module, whilethe feed stream is separated into two: a permeate stream and a retentatestream.

In the present Examples 2 and 3, the PPO concentration in both thepermeate stream and the retentate stream were monitored. Theseconcentrations were determined in the same way as in Example 1 andComparative Examples 1 and 2 and are shown in Table 2, as well as thePPO concentration of the feed. During the entire experimental period,the trans-membrane pressure was 5 bar and the temperature was roomtemperature. The total membrane surface of the membrane used in Examples2 and 3 was 1 m².

TABLE 2 Ex. 2 Ex. 3 PPO concentration in feed (ppmw) 116 4.9 PPOconcentration in permeate (ppmw) 2.8 0.06 PPO rejection (%) 98 99 PPOconcentration in retentate (ppmw) 153 6.4

Each of the experiments from Examples 2 and 3 was performed continuouslyduring seven days. The permeability, flux, permeate flow velocity andretentate flow velocity were stable during that entire experimentalperiod. In addition, the PPO rejection was stable.

From Table 2 it can be seen that the PPO rejection in Examples 2 and 3is relatively high, almost 100%. This implies that the permeatesobtained might be used as raw material in making a polyether polyol tobe used in making moulded polyurethane foam. Indeed, the permeateobtained in Example 3 may suitably be used in the production of mouldedpolyurethane foam. Said permeate only contained 0.06 ppmw of PPO havinga molecular weight of 20,000 and higher. However, the permeate obtainedin Example 2 which originated from a more contaminated PO feed, is notsuitable for use in the production of moulded polyurethane foam as itstill contains too much PPO, more in particular 2.8 ppmw of PPO having amolecular weight of 20,000 and higher. This is far above 0.4 ppmw whichin general is considered as the maximum allowable concentration of PPOhaving a molecular weight of 20,000 and higher, in PO to be used in theproduction of moulded polyurethane foam.

In addition to achieving a high PPO rejection during the entireexperimental period, another advantage of the membrane used in the abovespiral wound membrane module is that the permeability and flux remain atthe same level during the entire experimental period. There was noquestion of plugging or clogging of said membrane.

1. A process for removing poly(propylene oxide) from a propylene oxideby membrane separation, wherein a membrane having an average pore sizeof from 0 to 5 nm is used, which membrane is a polymeric membrane madefrom a polysiloxane which contains repeating units of the formula (I)—Si(R)(R′)—O—  (I) wherein R and R′ may be the same of different andrepresent hydrogen or a hydrocarbon group selected from the groupconsisting of alkyl, aralkyl, cycloalkyl, aryl, and alkaryl.
 2. Aprocess according to claim 1, wherein a liquid feed comprising propyleneoxide and poly(propylene oxide) is separated by the membrane into apermeate comprising propylene oxide and either no poly(propylene oxide)or poly(propylene oxide) at a concentration which is lower than thepoly(propylene oxide) concentration in the feed, and a retentatecomprising propylene oxide and poly(propylene oxide) at a concentrationwhich is higher than the poly(propylene oxide) concentration in thefeed.
 3. A process according to claim 2, wherein the poly(propyleneoxide) concentration in the permeate is from zero to at most 3 ppmw, onthe basis of total weight of the permeate.
 4. A process according toclaim 2, wherein the poly(propylene oxide) concentration in the permeateis from zero to less than 1 ppmw, on the basis of total weight of thepermeate.
 5. A process according to claim 3, wherein the permeate is foruse as raw material in making a polyether polyol to be used in makingslabstock polyurethane foam.
 6. A process according to claim 4, whereinthe permeate is for use as raw material in making a polyether polyol tobe used in making moulded polyurethane foam.
 7. A process according toclaim 2, wherein the poly(propylene oxide) concentration in theretentate is from zero to at most 3 ppmw, on the basis of total weightof the retentate.
 8. A process according to claim 7, wherein theretentate is for use as raw material in making a polyether polyol to beused in making slabstock polyurethane foam.
 9. A process according toclaim 1, wherein the separation is carried out at a temperature in therange of from 5 to 30° C.
 10. A process according to claim 4, whereinthe permeate is for use as raw material in making a polyether polyol tobe used in making slabstock polyurethane foam.